Active substance combinations having insecticidal and acaricidal properties

Description of the invention

The invention relates to pesticides which contain the known cyclic ketoenols on the one hand and other known insecticidal active substances on the other hand and which are very well suited for use in controlling animal pests such as insects and undesirable mites.

The invention also relates to a process for the production of pesticides.

Certain cyclic ketoenols are known to have herbicidal, insecticidal and acaricidal properties. The activity of these substances is good, but at low doses it is in some cases unsatisfactory.

Known for their herbicidal, insecticidal or acaricidal activity are unsubstituted, bicyclic 3-aryl-pyrrolidine-2,4-diones (EP-A-355599 and EP-A-415211) and substituted monocyclic 3-aryl-pyrrolidine-2 derivatives, 4-diones (EP-A-377893 and EP-A-442077).

Moreover, polycyclic derivatives of 3-arylpyrrolidine-2,4-diones are known (EP-A-442073) and derivatives of 1H-arylpyrrolidine-diones (EP-A-456063, EP-A-521334, EP-A-596298, EP-A -613884, EP-A-613885, WO 94/01997, WO 95/26954, WO 95/20572, EP-A-0668267, WO 96/25395, WO 96/35664, WO 97/01535, WO 97/02243, WO 97/36868, WO 97/43275, WO 98/05638, WO 98/06721, WO 98/25928, WO 99/16748, WO 99/24437, WO 99/43649, WO 99/48869 and WO 99/55673) .

It is further known that numerous heterocycles, organotin compounds, benzoylureas and pyrethroids have insecticidal and acaricidal properties (e.g. WO 93/22297, WO 93/10083, DE-A-2641343, EP-A-347488, EP- A-210487, US 3,364,177 and EP-A-234045). The action of these compounds, however, is not always satisfactory.

Nicotinergic acetylcholine receptor agonists and antagonists are a very well known group of compounds described, for example, in the following publications:

European Patent Nos: 464830, 428941, 425978, 386565, 383091, 375907, 364844, 315826, 259738, 254859, 235725, 212600, 192060, 163855, 154178, 136636, 136686, 303570, 302833, 306696, 189972, 455000 135956, 471372, 302389, 428941, 376279, 493369, 580553, 649845, 685477, 483055, 580553;

German Published Patent Nos. 3639877, 3712307;

Japanese Published Patent Nos .: 03220176, 02207083, 63307857, 63287764,

03246283, 049371, 03279359, 03255072, 05178833, 07173157, 08291171; US patents US Am. no: 5034524, 4948798, 4918086, 5039686, 5034404, 5532 365; PCT Application Nos. WO 91/17659, 91/4965;

French Patent Application No. 2,611,114; Brazilian Patent Application No. 8803621.

These compounds are included in part under the terms of nitromethylenes, nitrimines and their related compounds.

These compounds can advantageously be represented together by formula II

<img file="PL204252B1_D0001.tif" />

wherein

R is hydrogen, an optionally substituted acyl, alkyl, aryl, aralkyl, heterocyclyl, heteroaryl or heteroarylalkyl group,

A 'is a monofunctional group consisting of a hydrogen atom, an acyl, alkyl, aryl group, or a bifunctional group which is linked to Z',

E 'is the electron withdrawing group,

X 'represents the group -CH = or = N-, the group -CH = may be attached to the residue of Z' in place of a hydrogen atom,

Z 'is a monofunctional group from the series consisting of alkyl, -OR, -SR,

And the R substituents may be the same or different and have the meaning given above, or represent a bifunctional group which is linked to the residue A 'or to the residue X'.

In particular, in the case of nicotinergic acetylcholine receptor agonists and antagonists, the following compounds are mentioned as well known compounds:

<img file="PL204252B1_D0002.tif" />

PL 204 252 B1

<img file="PL204252B1_D0003.tif" />

PL 204 252 B1

<img file="PL204252B1_D0004.tif" />

Very particularly known agonists and antagonists of nicotinergic acetylcholine receptors are compounds with the following formulas:

PL 204 252 B1

N-CH

N-NO

CH

N

CH

CH ch₃

-Ń-C-CH fl

CN

C.

N

NHCH

N

CH

N-CH

N-NO

CH

NHCH

WELL

NHCH

CH

CH

WELL

CH- N

<img file="PL204252B1_D0005.tif" />

PL 204 252 B1

It has been found that mixtures consisting of compounds of formula I

<img file="PL204252B1_D0006.tif" />

wherein

W is a hydrogen atom, a C1-C4-alkyl group,

X is a C1-C4-alkyl group,

Y is a C1-C4-alkyl group,

Z represents a hydrogen atom, a C1-C4-alkyl group,

R is a C1-C4-alkoxy group,

G represents a hydrogen atom, a CO2-C1-C4-alkyl group and the formula II selected from a particular group of compounds exhibit a synergistic effect and are suitable for controlling animal pests.

The invention therefore relates to a pesticide, characterized in that it contains a synergistically active mixture of compounds of formula I

<img file="PL204252B1_D0007.tif" />

wherein

W is a hydrogen atom, a C1-C4-alkyl group,

X is a C1-C4-alkyl group,

Y is a C1-C4-alkyl group,

Z represents a hydrogen atom, a C1-C4-alkyl group,

R is a C1-C4-alkoxy group,

G is a hydrogen atom, a CO2-C1-C4-alkyl group and the formula II is selected from the following compounds:

<img file="PL204252B1_D0008.tif" />

PL 204 252 B1

<img file="PL204252B1_D0009.tif" />

Particularly preferred is an agent which comprises the following compounds of formula I, wherein W, X, Y, Z, R and G are as given in the following table:

<td>IN</td><td>X</td><td>Y</td><td>WITH</td><td>R</td><td>G.</td>

<td>H.</td><td>CH3</td><td>5-CH3</td><td>H.</td><td>OCH3</td><td>CO2-C2H5</td>

<td>CH3</td><td>CH3</td><td>3-CH3</td><td>4-CH3</td><td>OCH3</td><td>H.</td>

It is preferred that the composition comprises a mixture of compounds of formula I and formula II in a ratio of 1: 100 to 100: 1.

The invention also relates to the use of a synergistically active mixture comprising compounds of formula I and formula II as defined above for controlling animal pests.

Another object of the invention is a process for the preparation of pest control agents, characterized in that a synergistically active mixture containing compounds of formula I and formula II is mixed with diluents and / or surfactants.

Depending on the type of substituents, the compounds of formula I can also exist as geometric and / or optical isomers or isomer mixtures of various compositions, and can, if appropriate, be separated in a known manner. Both the pure isomers and mixtures of isomers, their preparation and use thereof, and compositions containing them are an object of the invention. For the sake of simplicity, however, only the compounds of formula I are mentioned hereinafter, although this includes both pure compounds and, if appropriate, also mixtures with different proportions of isomeric compounds.

Also particularly preferred are compositions according to the invention which contain mixtures containing compounds of the formulas Ila, IIk.

Furthermore, mixtures containing compounds of the formulas Ile, IIg, IIh, III, IIm are particularly preferred.

Also preferred are active compound mixtures according to the invention containing the following compounds of formula I

PL 204 252 B1

<img file="PL204252B1_D0010.tif" />

<td>Example no</td><td>IN</td><td>X</td><td>Y</td><td>WITH</td><td>R</td><td>G.</td><td>Melting point ° C</td>

<td>I-3</td><td>H.</td><td>CH3</td><td>5-CH3</td><td>H.</td><td>OCH3</td><td>H.</td><td> &gt;220</td>

<td>I-13</td><td>H.</td><td>CH3</td><td>4-CH3</td><td>5-CH3</td><td>C2H5</td><td>CO-n-Pr</td><td> 134</td>

<td>I-14</td><td>H.</td><td>CH3</td><td>4-CH3</td><td>5-CH3</td><td>OC2H5</td><td>CO-i-Pr</td><td> 108</td>

<td>I-15</td><td>H.</td><td>CH3</td><td>4-CH3</td><td>5-CH3</td><td>OC2H5</td><td>CO-c-Pr</td><td> 163</td>

It is also possible to use the following compounds of the formula I in the active compound combinations

<td>Example no</td><td>IN</td><td>X</td><td>Y</td><td>WITH</td><td>R</td><td>G.</td><td>Melting point ° C</td>

<td>I-1</td><td>H.</td><td>Br</td><td>5-CH3</td><td>H.</td><td>OCH3</td><td>CO-i-C3Hy</td><td> 122</td>

<td>I-2</td><td>H.</td><td>Br</td><td>5-CH3</td><td>H.</td><td>OCH3</td><td>CO2-C2H5</td><td> 140-142</td>

<td>I-5</td><td>CH3</td><td>CH3</td><td>3-Br</td><td>H.</td><td>OCH3</td><td>H.</td><td> &gt;220</td>

<td>I-6</td><td>CH3</td><td>CH3</td><td>3-Cl</td><td>H.</td><td>OCH3</td><td>H.</td><td> 219</td>

<td>I-7</td><td>H.</td><td>Br</td><td>4-CH3</td><td>5-CH3</td><td>OCH3</td><td>CO-i-C3Hy</td><td> 217</td>

<td>I-8</td><td>H.</td><td>CH3</td><td>4-Cl</td><td>5-CH3</td><td>OCH3</td><td>CO2C2H5</td><td> 162</td>

<td>I-9</td><td>H.</td><td>CH3</td><td>4-CH3</td><td>5-CH3</td><td>OCH3</td><td>With ““ \ CO —_ ^ 0</td><td>Oil</td>

<td>I-11</td><td>H.</td><td>CH3</td><td>5-CH3</td><td>H.</td><td>C2H5</td><td>With ““ \ co —_ ^ 0</td><td>Oil</td>

<td>I-12</td><td>CH3</td><td>CH3</td><td>3-Br</td><td>H.</td><td>OC2H5</td><td>COH-C3H7</td><td> 212-214</td>

The active compound combinations with good plant tolerance and low toxicity to warm-blooded animals are suitable for the control of animal pests, in particular insects, arachnids and nematodes, which occur in agriculture, forests, in the conservation of stocks and materials, and in the field of hygiene and veterinary medicine. They can advantageously be used as plant protection agents. They are active against normally sensitive and resistant species and against all or some developmental stages. The above-mentioned pests include:

from the order of Isopoda, e.g. Oniscus asellus, Armadillidium vulgare, Porcellio scaber; from the order of the Diplopoda, for example, Blaniulus guttulatus; from the class of the Chilopoda, e.g. Geophilus carpophagus, Scutigera spec; from the order of the Symphyla, e.g. Scutigerella immaculata; of the order of Thysanur, for example Lepisma saccharina; from the order Collembola, e.g. Onychiurus armatus;

From Orthoptera, e.g., Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus spp., Schistocerca gregaria;

from the order Blattaria, for example Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blatella germanica;

of the order of the Dermaptera, for example, Forficula auricularia; from the order Isoptera, for example Reticulitermes spp .;

from the order of Phthiraptera, e.g. Pediculus humanus corporis, Haematopinus spp., Linognathus spp. Trichodectes spp., Damalinia spp.

from the order of the Thysanoptera, e.g. Hercinothrips femoralis, Thrips tabaci, Thrips palmi, Frankliniella occidentalis;

from the order Heteroptera, e.g., Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp .;

from the Homopter series, e.g. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus spp. Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp .; from the order Lepidoptera, e.g. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella xylostella, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurlocelisis, Phyla spp., Bucculatrix thurlocielisisp. spp., Mamestra brassicae, Panolis flammea, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana, Cnaphalocerus spp., Oulema oryzae;

of the Coleopteran order, e.g. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa ​​decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilzahensna spp., Otilliodes chrysocephala, Epilzahensna spp. sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica, Lissorhoptrus oryzophilus;

from the order of the Hymenoptera, e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.

from the class of Diptera, e.g. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp. , Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa, Hyliriomyza spp., Lemyia spp. ;

from the class of the Siphonaptera, for example Xenopsylla cheopis, Ceratophyllus spp.; from the class of Arachnida e.g. Scorpio maurus, Latrodectus mactans, Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp. , Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranyus spp., Hemitarsonemus spp., Brevipalpus spp.

Plant parasite nematodes include, for example, Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longiduschinema spp., Xiphinema spp., Xiphinema spp. spp ..

According to the invention, it is possible to treat all plants and parts of plants. Plants are understood to mean all plants and plant populations, such as desired and undesirable wild plants or crops (including naturally occurring crops). Crop plants can be plants which are obtained by conventional methods of breeding and optimization, or by means of biotechnological and gentechnological methods or a combination of these methods, including transgenic plants and including plant varieties protected or not protected by variety rights. Parts of plants are understood to mean all above-ground and underground parts

And plant organs such as shoots, leaves, flowers and roots, mentioning, for example, leaves, needles, stalks, trunks, flowers, fruit, fruit and seeds, and also roots , buds and rhizomes. Parts of plants also include harvest and vegetative and generative propagation material, for example cuttings, buds, rhizomes, ablegiers, and seeds.

According to the invention, the treatment of the plants and plant parts with the compounds of the formula I alone, in particular with combinations of active substances, is carried out either directly or by treating the surroundings, the environment or the storage space according to known treatment methods, e.g. by means of dipping, spraying, steaming, nebulizing, scattering, coating, and in the case of propagation material, especially in the case of seeds, also by means of producing single or multi-layer coatings.

As mentioned above, it is possible to treat all plants and their parts according to the invention. In a preferred embodiment, wild-occurring or obtained by conventional biological breeding methods such as crossing or protoplast fusion, plant species and plant cultivars, and parts thereof are treated. According to a further preferred embodiment, transgenic plants and plant cultivars which are obtained by gentechnological methods, if appropriate in combination with conventional methods (Genetic Modified Organisms), and parts thereof are treated. The term plant parts or parts or plant parts has been explained above.

The plant species which are commercially or in general use are particularly preferably treated according to the invention.

Depending on the plant types or plant varieties, their location and growth conditions (soil, climate, growing season, fertilization), super-additive (synergistic) effects may also occur during the treatment according to the invention. For example, lower dosages and / or a broadening of the action spectrum and / or an enhancement of the action of the substances and agents used according to the invention are possible, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to the salt content of the invention. water or soil, increased flowering, easier harvesting, faster ripening, higher yields, higher quality and / or higher nutritional value of harvested products, a higher storage capacity and / or processing capacity of the harvested products, the effects of which are actually beyond the expected effects.

The plants or varieties of transgenic plants (obtained by gentechnology) preferably treated according to the invention include all plants which, by means of gentechnological modification, obtain genetic material which gives these plants particularly advantageous properties (traits). Examples of such properties are improved plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or salt content in water or soil, increased flowering, easier harvesting, faster ripening, higher yields, higher quality and / or higher nutritional value of harvested products, higher storage capacity and / or processing capacity of harvested products. Further and particularly important examples of such properties are the increased resistance of plants to animal and microbial pests such as insects, mites, fungi, plant pathogens, bacteria and / or viruses, and the increased tolerance of plants to certain herbicidal active compounds. Examples of transgenic plants are, in particular, important crops such as cereals (wheat, rice), corn, soybeans, potatoes, cotton, rapeseed and fruit plants (with fruits such as apples, pears, citrus fruits and grapes), the especially maize, soybean, potatoes, cotton and rapeseed are mentioned. The properties (features) are, in particular, the increased resistance of plants to insects due to toxins produced in the plant, in particular those produced by genetic material from Bacillus Thuringiensis (e.g. by the CrylA (a), CrylA (b), CrylA (c) genes. ), CryllA, CrylllA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CrylF and combinations thereof) (hereinafter referred to as Bt plants). As properties (characteristics), moreover, the increased tolerance of the plants to certain herbicidal active compounds, for example imidazolinones, sulfonylureas, glyphosates or phosphinothricin (e.g. the PAT gene), are mentioned in particular. The genes which provide the desired properties (traits) in each case can also be combined with each other in transgenic plants. Examples of Bt plants are maize varieties, cotton varieties, soybean varieties and potato varieties which are distributed under the trade names YIELD GARD® (e.g. corn, cotton, soybeans), KnockOut® (e.g. corn), StarLink® (e.g. maize), Bollgard® (cotton), Nucotn® (cotton) and NewLeaf® (potatoes). Examples of herbicide tolerant crops include corn varieties, cotton varieties and soybean varieties which are known under the trade names Roundup Ready® (glyphosate tolerance e.g. corn, cotton, soybeans), Liberty Link®

Phosphinothricins, e.g. rapeseed), IMI® (imidazolinone tolerance) and STS® (sulfonylurea tolerance, e.g. corn). The cultivars marketed under the name Clearfield® (e.g. corn) are also mentioned as herbicide tolerant plants (conventionally bred for herbicide tolerance). Of course, the above statements also apply to plant varieties which are developed in the future or supplied to the market in the future, with these or future developed genetic properties (traits).

The plants listed can be treated particularly advantageously according to the invention with the active compound mixtures according to the invention. The preferred ranges stated above for the mixtures also apply to the treatment of such plants. It is particularly advantageous to treat the plants with the mixtures mentioned in this specification as being particularly advantageous.

The ratio of compounds of formula I and compounds of formula II introduced and the total amount of the mixture depends on the nature and presence of the insects. Optimal ratios and total doses can be established with each use by means of a number of tests. In general, the ratio of compounds of formula I and compounds of formula II is 1: 100 to 100: 1, preferably 1:25 to 25: 1, especially 1: 5 to 5: 1. These are parts by weight.

The active ingredient combinations can be converted into known preparations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension / emulsion concentrates, natural and synthetic substances impregnated with the active ingredient and fine capsules in the substances. polymeric.

These preparations are prepared in a manner known per se, for example by mixing the active ingredients with diluents, i.e. liquid solvents and / or solid carriers, optionally with the use of surfactants, i.e. emulsifiers and / or dispersants and / or foaming agents.

In the case of the use of water as an extender, it is also possible, for example, to use organic solvents as auxiliary solvents. Suitable liquid solvents are in principle aromatic compounds such as xylene, toluene or alkyl naphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.

Suitable solid carriers are, for example, ammonium salts and natural rock powders, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic minerals, such as highly dispersed silicic acid, aluminum oxide. and silicates; as solid carriers for granules, e.g. crushed and fractionated natural minerals such as calcite, marble, pumice stone, sepiolite, dolomite and synthetic granules from inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, corn cob and tobacco stalks; as emulsifying and / or foaming agents, e.g. non-ionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates; as dispersants, for example, lignin sulfite liquors and methylcellulose are mentioned.

Adhesion promoters such as carboxymethyl cellulose, natural and synthetic powdered, granular or latex polymers such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids such as cephalin and lecithin, and synthetic phospholipids may be used in the formulations. Other additives can be mineral and vegetable oils.

Dyes such as inorganic pigments such as iron oxide, titanium oxide, ferric cyan blue, and organic dyes such as alizarin, azo and metallophthalocyanine dyes, as well as trace nutrients such as iron, manganese, boron, copper, cobalt salts can also be used. , molybdenum and zinc.

The formulations generally contain 0.1-95% by weight of active ingredient, preferably 0.5-90%.

The active compound combinations according to the invention can be in the form of commercial preparations and in use forms prepared from these preparations in admixture with other active substances, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth regulators or herbicides. The insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms, and others.

The following substances are used, for example, as particularly advantageous mixture components: Fungicides:

aldimorph, ampropylphos, ampropylphosopotassium, andoprim, anilazine, azaconazole, azoxystrobin, benalaxyl, benodanil, benomyl, benzamacryl, isobutylbenzamacryl, bialaphos, binapacryl, biphenyl, bitertrimanil, basticidinazol, basticidinazole, basticidinazole , captafol, captan, carbendazim, carboxin, carvone, quinomethionate (Quinomethionate), chlobenthiazone, chlorophenazole, chloroneb, chloropicrin, chlorothalonil, chlozolinate, closetacone, kufraneb, cymoxanil, cyproconazole, cyprodinil, ciprofuram, debacarb, dichlorophen, diclobutrazole, diclofluanid, diclomesine, dicloran, diethofencarb, diphenoconazole, dimethirimol, dimethomorph, diniconazole, diniconazole-M, dinocapyram, debacarb, diphenylamine, diphenylamine, diclosine epoxiconazole, etaconazole, ethirimol, etridiazole, famoxadone, fenapanil, fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, flumetover, fluoromide, fluchinconazole, flurprimidol, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminum, fosetyl-sodium, phthalide, fuberidazole, furalaxyl, furamethpir, furazocycarolisil, furazocycarolisil hexachlorobenzene, hexaconazole, hymexazole, imazalil, imibenconazole, iminooctadine, iminooctadine albesilate, iminooctadine triacetate, iodocarb, ipconazole, iprobenphos (IBP), iprodione, irumamycin, isopedrothion, kasugamycin, methyl-cresoxime, copper preparations such as copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, Cu-oxine and Bordeaux mixture, mancoper, mancozeb, maneb, meferimzone, mepanipyrim, mepronil, metalaxyl, metasulfonocarbolaxyl , metfuroxam, metiram, metomeclam, metsulfovax, mildiomycin, myclobutanil, myclosoline, nickel dimethyldithiocarbamate, isopropyl nitrotal, nuarimol, ofurace, oxadixyl, oxamocarb, oxolinic acid, oxycarboxime, oxypenthiine, paclobutrazole, perfurazoate, penconazole, pencycuron, phosdifene, pimaricin, piperalin, polyoxin, polyoxorim, probenazole, prochloraz, procimidone, propamocarb, propanosine sodium, propanosine, propanonetrazole, pyryconetanazole, propanosine, pyrimiconphosinbosinebibinib chintocene (PCNB), sulfur and sulfur preparations, tebuconazole, teclophtalam, tecnazene, tetcyclacis, tetraconazole, thiabendazole, thicofen, thifluzamide, methylthiophanate, thiram, thioximide, methyl tolclophos, tolylfluanid, triadimhephon, triadimenol, triazobutyl, triazoxide, trichlamide, tricyclazole, tridemorph, triflumizole, triforine, triticonazole, uniconazole, validamycin A, vinclozoline, viniconazole, zineb, zineagger, and ziram,

OK-8705,

OK-8801, α- (1,1-dimethylethyl) -e- (2-phenoxyethyl) -1H-1,2,4-triazole-1-ethanol, a- (2,4-dichlorophenyl) -e-fluoro- b-propyl-1H-1,2,4-triazole-1-ethanol, α- (2,4-dichlorophenyl) -e-methoxy-α-methyl-1H-1,2,4-triazole-1-ethanol, a- (5-methyl-1,3-dioxan-5-yl) -e - [[4- (trifluoromethyl) -phenyl] -methylene] -1H-1,2,4-triazole-1-ethanol, (5RS , 6RS) -6-hydroxy-2,2,7,7-tetramethyl-5- (1H-1,2,4-triazol-1-yl) -3-octanone, (E) -a- (methoxyimino) - N-methyl-2-phenoxy-phenylacetamide, {2-methyl-1 - [[[1- (4-methylphenyl) ethyl] -amino] carbonyl] propyl} carbamic acid 1-isopropyl ester,

O- (phenylmethyl) oxime 1- (2,4-dichlorophenyl) -2- (1H-1,2,4-triazol-1-yl) -ethanone,

1- (2-methyl-1-naphthalenyl) -1H-pyrrole-2,5-dione,

1- (3,5-dichlorophenyl) -3- (2-propenyl) -2,5-pyrrolidinedione,

1 - [(diiodomethyl) sulfonyl] -4-methyl-benzene,

1 - [[2- (2,4-dichlorophenyl) -1,3-dioxolan-2-yl] methyl] -1H-imidazole,

PL 204 252 B1

1 - [[2- (4-chlorophenyl) -3-phenyloxiranyl] methyl] -1H-1,2,4-triazole,

1- [1- [2 - [(2,4-dichlorophenyl) methoxy] phenyl] ethenyl] -1H-imidazole,

1-methyl-5-nonyl-2- (phenylmethyl) -3-pyrrolidinol],

2 ', 6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoromethyl-1,3-thiazole-5-carboxanilide,

2,2-dichloro-N- [1- (4-chlorophenyl) ethyl] -1-ethyl-3-methyl-cyclopropanecarboxamide, 2,6-dichloro-5- (methylthio) -4-pyrimidinyl thiocyanate,

2,6-dichloro-N- (4-trifluoromethylbenzyl) -benzamide,

2,6-dichloro-N - [[4- (trifluoromethyl) phenyl] methyl] benzamide,

2- (2,3,3-triiodo-2-propenyl) -2H-tetrazole,

2 - [(1-methylethyl) sulfonyl] -5- (trichloromethyl) -1,3,4-thiadiazole,

2 - [[6-deoxy-4-O- (4-O-methyl-eD-glycopyranosyl) -aD-glucopyranosyl] amino] -4-methoxy-1H-pyrrolo [2,3-d] pyrimidine 5-carbonitrile ,

2-aminobutane,

2-bromo-2- (bromomethyl) pentanedinitrile,

2-chloro-N- (2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl) -3-pyridinecarboxamide,

2-chloro-N- (2,6-dimethylphenyl) -N- (isothiocyanatomethyl) -acetamide,

2- phenylphenol (OPP),

3.4- dichloro-1- [4- (difluoromethoxy) -phenyl] -1H-pyrrole-2,5-dione,

3.5- dichloro-N- [cyano - [(1-methyl-2-propynyl) oxy] methyl] benzamide,

3- (1,1-dimethylpropyl-1-oxo-1H-indene-2-carbonitrile,

3- [2- (4-chlorophenyl) -5-ethoxy-3-isoxazolidinyl] pyridine,

4- chloro-2-cyano-N, N-dimethyl-5- (4-methylphenyl) -1H-imidazole-1-sulfonamide,

4-methyl-tetrazolo [1,5-a] quinazolin-5 (4H) -one,

8- (1,1-dimethylethyl) -N-ethyl-N-propyl-1,4-dioxaspiro [4.5] decane-2-methanamine, 8-hydroxyquinoline sulfate,

9H-xanthene-9-carboxylic acid 2- [(phenylamino) carbonyl] -hydrazide,

Bis- (1-methylethyl) 3-methyl-4 - [(3-methylbenzoyl) -oxy] -2,5-thiophenedicarboxylate, cis-1- (4-chlorophenyl) -2- (1H-1,2,4- triazol-1-yl) -cycloheptanol, cis-4- [3- [4- (1,1-dimethylpropyl) -phenyl-2-methylpropyl] -2,6-dimethyl-morpholine hydrochloride,

[(4-chlorophenyl) azo] cyanoacetate, potassium bicarbonate, sodium methanetetrathiol,

Methyl 1- (2,3-dihydro-2,2-dimethyl-1H-inden-1-yl) -1H-imidazole-5-carboxylate,

Methyl N- (2,6-dimethylphenyl) -N- (5-isoxazolylcarbonyl) -DL-alaninate,

Methyl N- (chloroacetyl) -N- (2,6-dimethylphenyl) -DL-alaninate,

N- (2,3-dichloro-4-hydroxyphenyl) -1-methylcyclohexanecarboxamide,

N- (2,6-dimethylphenyl) -2-methoxy-N- (tetrahydro-2-oxo-3-furanyl) -acetamide,

N- (2,6-dimethylphenyl) -2-methoxy-N- (tetrahydro-2-oxo-3-thienyl) -acetamide,

N- (2-chloro-4-nitrophenyl) -4-methyl-3-nitro-benzenesulfonamide,

N- (4-cyclohexylphenyl) -1,4,5,6-tetrahydro-2-pyrimidinamine,

N- (4-hexylphenyl) -1,4,5,6-tetrahydro-2-pyrimidinamine,

N- (5-chloro-2-methylphenyl) -2-methoxy-N- (2-oxo-3-oxazolidinyl) -acetamide,

N- (6-methoxy) -3-pyridinyl) -cyclopropanecarboxamide,

N- [2,2,2-trichloro-1 - [(chloroacetyl) amino] ethyl] benzamide,

N- [3-chloro-4,5-bis- (2-propynyloxy) -phenyl] -N'-methoxymethanimidamide,

N-formyl-N-hydroxy-DL-alanine, sodium salt,

O, O-diethyl [2- (dipropylamino) -2-oxoethyl] -ethylphosphoramidothiolate, O-methyl-S-phenyl phenylphosphoramidothiolate,

S-methyl 1,2,3-benzothiadiazole-7-carbothiolate, spiro [2H] -1-benzopyran-2,1 '(3'H) -isobenzofuran-3'-one.

Bactericidal substances:

bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octilinone, furanecarboxylic acid, oxytetracycline, probenazole, streptomycin, teclophtalam, copper sulfate and other copper preparations.

PL 204 252 B1

Insecticides / acaricides / nematocides:

abamectin, acephate, acetamiprid, acrinathrin, alanycarb, aldicarb, aldoxycarb, alpha-cypermethrin, alphamethrin, amitraz, avermectin, AZ 60541, azadirachtin, azamethos, azinphos A, azinphos M, azocyclotin,

Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillus thuringiensis, baculoviren, Beauveria bassiana, Beauveria tenella, bendiocarb, benfuracarb, bensultap, benzoximate, betacyfluthrin, bifetryenazate, bifentanoforin, biopetrofencarbine, biopetanofencarbine , butylpyridaben, cadusaphos, carbaryl, carbofuran, carbofenothion, carbosulfan, kartap, chloetocarb, chlorethoxifos, chlorfenapyr, chlorfenvinphos, chlorofluazuron, chloromephos, chlorpyrifos, chlorpyrifos M, chlovaportrin, cis-resmetrin, cispermethrin, clocytrin, cloetocarb, clofentezine, cyanophos, cycloprene, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, sypermethrin, demethamethryn, demethrimethrin diafentiuron, diazinon, dichlorvos, diflubenzuron, dimethoate, dimethylvinphos, diophenolate, disulfoton, docusate-sodium, dofenapine, eflusilanate, emamectin, empentrin, endosulfan, entomophora spp., esphenvalerate, etiofencarb, etion, etoprofos, etofenprox, etoxazole, etrimfos, fenamiphos, fenazaquin, fenbutatin oxide, fenitrothione, fenothiocarb, fenoxacrim, fenoxycarb, fenpropathrin, fenpyrad, fenpyritrin, fenpyroximate, flufronilerincynin, fenpyrinvalerin , flutenazine, fluvalinate, phonophos, phosmetilan, fostiazate, fubfenprox, furathiocarb, granulosis viruses, halofenozide, HCH, heptenophos, hexaflumuron, hexythiazox, hydroprene, imidacloprid, isazophos, isofenphos, isoxanthione, ivermectin, polyhedral nuclei viruses, lambda-cyhalothrin, lufenuron, malathion, mecarbam, metaldehyde, methamidophos, Metharhizium anisopliae, Metharhizium flavoviride, metidation, methioxadifazhevectin, methaoxadhevizhebectin, methaoxadinbectinbectin , naled, nitenpyram, nithiazine, novaluron, ometoate, oxamyl, oxydemeton M,

Paecilomyces fumosoroseus, parathion A, parathion M, permethrin, phethoate, forat, phosalon, phosmet, phosphamidone, phoxime, pyrimicarb, pirimifos A, pirimifos M, profenophos, promecarb, propoxur, prothiophos, protoate, pymethrosin, pyentrummetrin, pyentrummetrin , pyridathione, pyrimidifene, pyriproxifene, chinalphos, ribavirin, salition, sebufos, silafluofen, spinosad, sulfotep, sulprophos, tau-fluvalinate, tebufenozide, tebufenpyrad, tebupirimifos, teflubenzuron, teminfoshthoshtriv terbufos, tetrachlorovinfos, teta-cypermethrin, thiamethoxam, thiapronil, thiatrifos, thiocyclamate hydrogen oxalate, thiodicarb, thiophanox, thuringiensin, tralocytrin, tralometrin, triaraten, triazamate, triazophos, triazophyllphenidinyl, triazamate, triazophoniclphenidin, triarate, triazophosum, triazophosphate, lecidin, triazamate, triazophoniclphenidin, triazamate, triazophyllphenidin.

YI 5302, zeta-cypermethrin, zolaprofos,

(1R-cis) - [5- (phenylmethyl) -3-furanyl] -methyl-3 - [(dihydro-2-oxo-3 (2H) -furanylidene) -methyl] 2,2-dimethylcyclopropanecarboxylate,

(3-phenoxyphenyl) methyl 2,2,3,3-tetramethylcyclopropanecarboxylate,

1- [(2-chloro-5-thiazolyl) -methyl] -tetrahydro-3,5-dimethyl-N-nitro-1,3,5-triazine-2 (1H) -imine,

2- (2-chloro-6-fluorophenyl) -4- [4- (1,1-dimethylethyl) -phenyl] -4,5-dihydroxazole,

2- (acetyloxy) -3-dodecyl-1,4-naphthalenedione,

2-chloro-N - [[[4- (1-phenylethoxy) phenyl] amino] carbonyl] benzamide,

2-chloro-N - [[[4- (2,2-dichloro-1,1-difluoroethoxy) -phenyl] -amino] -carbonyl] -benzamide, 3-methylphenyl propylcarbamate,

4- [4- (4-ethoxyphenyl) -4-methylpentyl] -1-fluoro-2-phenoxy-benzene,

4-chloro-2- (1,1-dimethylethyl) -5 - [[2- (2,6-dimethyl-4-phenoxyphenoxy) ethyl] thio] -3 (2H) -pyridazinone,

4-chloro-2- (2-chloro-2-methylpropyl) -5 - [(6-iodo-3-pyridinyl) -methoxy] -3 (2H) -pyridazinone,

4-chloro-5 - [(6-chloro-3-pyridinyl) methoxy] -2- (3,4-dichlorophenyl) -3 (2H) -pyridazinone,

PL 204 252 B1

Bacillus thuringiensis strain EG-2348,

Benzoic acid 2-benzoyl-1- (1,1-dimethylethyl) hydrazide, 2,2-dimethyl-3- (2,4-dichlorophenyl) -2-oxo-1-oxaspiro [4.5] dec-3-ene ester -4-yl butanoic acid,

[3 - [(6-chloro-3-pyridinyl) methyl] -2-thiazolidinylidene] -cyanamide, dihydro-2- (nitromethylene) -2H-1,3-thiazine-3 (4H) -carboxaldehyde, [2- Ethyl [[1,6-dihydro-6-oxo-1- (phenylmethyl) -4-pyridazinyl] -oxy] -ethyl] -carbamate, N- (3,4,4-trifluoro-1-oxo-3-butenyl) ) -glycine,

N- (4-chlorophenyl) -3- [4- (difluoromethoxy) -phenyl] -4,5-dihydro-4-phenyl-1H-pyrazole-1-carboxamide,

N - [(2-chloro-5-thiazolyl) methyl] -N'-methyl-N-nitroguanidine,

N-methyl-N '- (1-methyl-2-propenyl) -1,2-hydrazine dicarbothioamide,

N-methyl-N'-2-propenyl-1,2-hydrazine dicarbothioamide,

O, O-diethyl [2- (dipropylamino) -2-oxoethyl] ethylphosphoramidothiolate.

A mixture with other known active ingredients, such as weed adducts, or with fertilizers and growth regulators is also possible .

The active compound combinations according to the invention can also be mixed with synergistic substances when used as insecticides in the form of their commercial preparations and in the form of formulations made from these preparations. Synergistic substances are compounds by which the action of the active substances is enhanced without the added synergistic substance having to be active by itself.

The active ingredient content of the use forms prepared from the commercial preparations can be varied within wide limits. The active ingredient concentration of the use forms may be 0.0000001 to 95% by weight of active ingredient, preferably 0.0001-1% by weight.

The agents are used in a known manner adapted to the formulation.

When used against pests in the field of hygiene and stock protection, the active compound combinations are distinguished by an excellent residual action on wood and clay and a good alkali resistance on calcified substrates.

The active compound combinations according to the invention are active not only against plant pests, pests in the field of hygiene and in the protection of stocks, but also in the field of veterinary medicine against animal parasites (ectoparasites) such as shield ticks, skin ticks, mites, Trombicula mites, flies (stinging flies) and sucking), parasitic fly larvae, lice, hairlings, bird lice and fleas. These parasites include:

from the order Anoplurida e.g. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp., from the order Mallophagida and from the order Amblycerina and Ischnocerina e.g. Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp. Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp. ., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp., Melophagus spp., From the order Siphonapterida e.g. Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp., From the order Heteropterida e.g. Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp. Blattarida e.g. Blatta orientalis, Periplaneta americana, Blatella germanica, Supella spp., From the Acaria subclass (Acarida) and the Meta- and Mesostigmata orders e.g. Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp.,

Dermanyssus spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp., Varroa spp., Actinedida (Prostigmata) and Acaridida (Astigmata) e.g. Acarapis spp., Cheyletiella spp.,

Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptiopes spp. ., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., Laminosioptes spp.

PL 204 252 B1

The active compound combinations according to the invention are also suitable for controlling arthropods attacking farm animals, such as, for example, cattle, sheep, goats, horses, pigs, donkeys, camels, buffaloes, rabbits, chickens, turkeys, ducks, geese, bees, other animals. domestic animals such as, for example, dogs, cats, peace birds, aquarium fish, and so-called test animals, such as, for example, hamsters, guinea pigs, rats and mice. As a result of the control of these arthropods, the mortality and lowering of the yield (in the case of meat, milk, wool, hides, eggs, honey, etc.) are reduced, so that by using the active compounds according to the invention, more economic and simple animal husbandry is possible.

The active compound combinations according to the invention are used in the veterinary field in a manner known per se by enteral administration in the form of, for example, tablets, capsules, drinks, drains, granules, pastes, pills, via food, in the form of suppositories, by parenteral administration, such as by injection. (intramuscular, subcutaneous, intravenous, intraperitoneal and other), in the form of implants, by application to the nose, by dermal application in the form of, for example, dipping or bathing (Dippen), spraying (Spray), pouring (Pour-on and Spot-on), washing, powdering and using shaped articles containing the active substance, such as neck collars, earrings, tail earrings, limb bands, bridles, marking devices, etc.

For application to pigs, birds, domestic animals etc., the active ingredients can be administered as preparations (for example, powders, emulsions, flowables) containing the active ingredient in an amount of 1-80% by weight, either directly or at 100 to 10,000 times. by folding or as a chemical bath.

Furthermore, it has been found that the active compound combinations according to the invention have a strong insecticidal action against insects that decompose technical materials.

By way of example and preferably, but without limitation, the following insects are mentioned: beetles, such as Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, linear Lyctus africanis, Lyctus planictus, Lyctus planicoxus, Lyctus planicus, Lyctus planicus spec, Tryptodendron spec, Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec, Dinoderus minutus, Hymenoptera such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur, ants such as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus.

Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus, Bristle-Tails such as Lepisma saccharina.

In the present description, technical materials are understood to mean non-living materials, such as, in particular, plastics, adhesives, adhesives, papers and cardboard, leather, wood and wood products, and coating agents.

In particular, the material which is protected against attack by insects is wood and wood products.

The term wood and wood processing products that can be protected with the agents according to the invention or mixtures containing them include, for example, construction timber, wooden logs, railway sleepers, parts of bridges, boat decks, wooden vehicles, boxes, pallets, containers, telephone masts, wooden casings, wooden windows and doors, plywood, chipboards, carpentry products or wooden products, which are generally used in house construction or in construction carpentry.

The active compound combinations can be used as such, in the form of concentrates or in the form of generally known preparations, such as powders, granules, solutions, suspensions, emulsions or pastes.

The preparations mentioned can be obtained in a manner known per se, for example by mixing the active ingredients with at least one solvent or diluent, emulsifier, dispersant and / or a binding or fixing agent, a hydrophobic agent, optionally desiccants and UV stabilizers and, if appropriate, dyes and pigments, and further auxiliaries.

The insecticides or concentrates used for the protection of wood and wood products contain the active compound according to the invention in a concentration of 0.0001-95% by weight, in particular 0.001-60% by weight.

The amount of the agent or concentrate used depends on the type and presence of the insects and the environment. The optimal amount to be used can be determined in each case by the series te18

PL 204 252 B1. In general, however, an amount of 0.0001-20% by weight, preferably 0.001-10% by weight of active ingredient, based on the material to be protected, is sufficient.

As solvent and / or diluent, there is used an organic chemical solvent or solvent mixture and / or an oily or oily type low-volatile organic chemical solvent or solvent mixture and / or a polar organic chemical solvent or solvent mixture and / or water and optionally an emulsifier and / or an agent. wetting.

The organic chemical solvents used are preferably oily or oily type solvents with a volatility number above 35 and a flash point above 30 ° C, preferably above 45 ° C. Suitable mineral oils or their aromatic fractions or mixtures of solvents containing mineral oils, preferably ligroin, naphtha and / or alkylbenzenes, are suitable as such difficult-volatile, water-insoluble oily and oily solvents.

Preference is given to using mineral oils with a boiling range of 170-220 ° C, ligroin with a boiling range of 170-220 ° C, spindle oil with a boiling range of 250-350 ° C, kerosene or aromatics with a boiling range of 160-280 ° C. C, turpentine oil and the like.

A preferred procedure uses liquid aliphatic hydrocarbons with a boiling range of 180-210 ° C or high-boiling mixtures of aromatic and aliphatic hydrocarbons with a boiling range of 180-220 ° C and / or spindle oil and / or monochloronaphthalene, preferably α-monochloronaphthalene.

Organic slow-volatile oily or oil-type solvents with a volatility number above 35 and a flash point above 30 ° C, preferably above 45 ° C, may be partially replaced by highly or semi-volatile organic chemical solvents, but the solvent mixture should also have a volatility number above 35 and a flash point above 30 ° C, preferably above 45 ° C, and the insecticide-fungicide mixture is soluble or emulsifiable in this solvent mixture.

According to a preferred procedure, a portion of the organic chemical solvent or solvent mixture is replaced with an aliphatic polar organic chemical solvent or solvent mixture. Preference is given to using hydroxyl and / or ester groups and / or ether groups containing aliphatic chemical organic solvents, such as, for example, glycol ethers, esters or the like.

As organic chemical binders in the context of the present invention, use is made of the known synthetic resins that can be diluted with water and / or in the chemical organic solvents used, which are soluble or dispersible or emulsifiable and / or drying oils that bind, in particular binders consisting of or containing an acrylate resin. , vinyl resin, e.g. polyvinyl acetate, polyester resin, polycondensation or polyaddition resins, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin such as indene-coumarone resin, silicone resin, drying vegetable oils and / or drying oils and / or physically drying binders based on natural and / or synthetic resin.

The synthetic resin used as the binder can be introduced in the form of an emulsion, dispersion or solution. It is also possible to use bitumens or bituminous substances in an amount of up to 10% by weight as a binder. In addition, known dyes, pigments, hydrophobic agents, odor improvers and inhibitors or corrosion protection agents and the like can also be used.

According to the invention, the agent or concentrate preferably comprises, as organic chemical binder, at least one alkyd resin or a modified alkyd resin and / or a drying vegetable oil. Preferably according to the invention are used alkyd resins with an oil content of more than 45% by weight, in particular 50-68% by weight.

Said binder can be completely or partially replaced by a fixative (mixture) or plasticizer (mixture). These additives are intended to prevent volatilization of the active substances and crystallization or precipitation. Preferably, 0.01-30% of the binder is replaced (based on 100% of the binder used).

As plasticizers, compounds from the chemical class of phthalic acid esters such as dibutyl, dioctyl or benzylbutyl phthalate, phosphoric acid esters such as tributyl phosphate, adipic acid esters such as di- (2-ethylhexyl) adipate, stearates such as stearate are used butyl or amyl stearate, oleates such as butyl oleate, glycerol ethers or higher molecular weight glycol ethers, glycerol esters, and p-toluenesulfonic acid esters.

PL 204 252 B1

Fixatives are chemically based on polyvinyl alkyl ethers, such as, for example, polyvinyl methyl ether, or on ketones, such as benzophenone, ethylenebenzophenone.

Suitable solvent or diluent are, in particular, water, if appropriate in a mixture with one or more of the abovementioned organic chemical solvents or diluents, emulsifiers and dispersants.

Particularly effective protection of the wood is achieved by large-scale industrial impregnation methods, e.g. by vacuum, double vacuum or pressure methods.

The ready-to-use compositions can optionally contain further insecticides and, if appropriate, one or more fungicides.

The active compound combinations according to the invention can also be used to protect objects against fouling, in particular in the case of ship hulls, screens, nets, building elements, wharfs and signaling devices which are in contact with sea water or saltwater at the mouth of a river.

Fouling by sessile oligochaetes such as limestone chasmas and by shells and species of the Ledamorpha group (duck shells), such as the different species Lepas and Scalpellum, or by species of the Balanomorpha group (sea pox) such as Balanus or Pollicipes species, increases the frictional resistance of ships and consequently leads to an increased energy consumption and, moreover, due to frequent stay in dry dock, to a marked increase in operating costs.

In addition to fouling by algae, for example Ectocarpus sp. And Ceramium sp., Fouling by sedentary groups of entomostraka, which are collectively referred to as Cirripedia (mustachioed river crayfish), is of particular importance.

It has surprisingly been found that the active compound combinations according to the invention have an excellent anti-fouling effect.

By using the active ingredient combination according to the invention, it is possible to dispense with the introduction of heavy metals, such as e.g. bis- (trialkyltin) sulfides, tri-n-butyltin laurate, tri-n-butyltin chloride, copper (I) oxide, triethyltin chloride, tri-n-butyl- (2-phenyl-4-chlorophenoxy) -cin, tributyltin oxide , molybdenum disulfide, antimony oxide, polymers of butyl titanate, phenyl- (bis-pyridine) -bismuth chloride, tri-n-butyltin fluoride, manganese ethylene bis-thiocarbamate, zinc dimethyldithiocarbamate, zinc ethylene bis-thiocarbamate and zinc salts 2-pyridine thiol-1-oxide, bis-dimethyldithiocarbamoyl zinc ethylene bis-thiocarbamate, zinc oxide, copper (I) ethylene bis-dithiocarbamate, copper thiocyanate, copper naphthenate and tributyl tin halides, or the concentration of these compounds can be significantly reduced.

The ready-to-use anti-fouling paints can optionally contain other active substances, preferably algicides, fungicides, herbicides, molluscicides or other anti-fouling active substances.

Suitable components for combination in the anti-fouling agents according to the invention are preferably:

algicides such as 2-t-butylamino-4-cyclopropylamino-6-methylthio-1,3,5-triazine, dichlorophen, diuron, endothal, fentin acetate, isoproturon, metabenzthiazuron, oxyfluorfen, quinoclamine and terbuthrin;

fungicides such as benzo [b] thiophenecarboxylic acid cyclohexylamide S, S-dioxide, dichlofluanid, fluorpholpet, 3-iodo-2-propynyl butylcarbamate, tolylfluanid and azoles such as azaconazoles, methoconazoles, epoconazonoleazole, and toconazonazole ;

molluscicides such as fentin acetate, metaldehyde, methiocarb, nicklosamide, thiodicarb and trimethacarb;

or known anti-fouling active substances such as 4,5-dichloro-2-octyl-4-isothiazolin-3-one, diiodomethylparathrylsulfone, 2- (N, N-dimethylthiocarbamoylthio) -5-nitrothiazyl, potassium, copper, sodium and zinc-1-oxide, 2-pyridinethiol, pyridine-triphenylborane, tetrabutyldistannoxane, 2,3,5,6-tetrachloro-4- (methylsulfonyl) -pyridine, 2,4,5,6-tetrachloroisophthalonitrile, tetramethylthiuram disulfide and 2,4-acid imide , 6-trichloro-phenyl maleic.

The antifoulants used contain the active compound combinations according to the invention in a concentration of 0.001-50% by weight, in particular 0.01-20% by weight.

PL 204 252 B1

The anti-fouling agents of the invention further contain known ingredients as described, for example, in Ungerer, Chem. Indium. 1985, 37, 730-732 and Williams, Antifouling Marine Coatings, Noyes, Park Ridge, 1973.

Anti-fouling coatings contain, in particular, binders in addition to active algaecides, fungicides, molluscicides and insecticides.

Examples of known binders are polyvinyl chloride in the solvent system, chlorinated rubber in the solvent system, acrylic resins in the solvent system, in particular in the water system, vinyl chloride / vinyl acetate copolymer systems in the form of aqueous dispersions or in the form of organic solvent systems, rubber with butadiene / styrene / acrylonitrile system, drying oils such as linseed oil, resin esters or modified hard resins in combination with tar or bitumen, asphalt and epoxy compounds, small amounts of chlorinated rubber, chlorinated polypropylene and vinyl resins.

The coating compositions optionally also contain inorganic pigments, organic pigments or dyes, which are preferably insoluble in seawater. In addition, the coating compositions may contain substances such as rosin to allow for a controlled release of the active ingredients. In addition, the coating compositions can contain plasticizers, modifying agents influencing rheology and other known ingredients. The active compound combinations according to the invention can also be incorporated into self-polishing antifoulants.

The active compound combinations according to the invention are also suitable for controlling animal pests, in particular insects, arachnids and mites, which occur in closed rooms such as, for example, apartments, factory halls, offices, vehicle cabins and the like. They can be used to control these pests in household insecticide products alone or in combination with other active ingredients or adjuvants. They are active against sensitive and resistant species and against all developmental stages. These pests include:

from the class of the Scorpionidea, for example, Buthus occitanus;

from the class of the Acarina e.g. Argas persicus, Argas reflexus, Bryobia ssp., Dermanyssus gallinae, Glyciphagus domesticus, Ornithodorus moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi, Neutrombicula autumnalis, Dermatophagoides pteronissimides forermatinae;

from the class of the Araneae, for example Aviculariidae, Araneidae;

from the class of the Opiliones, e.g. Pseudoscorpiones chelifer, Pseudoscorpiones cheiridium, Opiliones phalangium;

from the class of the Isopoda, for example, Oniscus asellus, Porcellio scaber; from the class of the Diplopoda, for example, Blaniulus guttulatus, Polydesmus spp .; from the class of the Chilopoda, for example Geophilus spp .;

from the order of the Zygentoma, e.g. Ctenolepisma spp., Lepisma saccharina, Lepismodes inquilinus; from the order of the Blattaria, e.g. Blatta orientalies, Blattella germanica, Blattella asahinai, Leucophaea maderae, Panchlora spp., Parcoblatta spp., Periplaneta australasiae, Periplaneta americana, Periplaneta brunnea, Periplaneta fuliginosa, Supella longipalpa;

from the class of Saltatoria, for example, Acheta domesticus; from the class of the Dermaptera, for example, Forficula auricularia; from the class of the Isoptera, e.g. Kalotermes spp., Reticulitermes spp; from the class of the Psocoptera, e.g. Lepinatus spp., Liposcelis spp.;

from the class of Coleptera, e.g. Anthrenus spp., Attagenus spp., Dermestes spp., Latheticus oryzae, Necrobia spp., Ptinus spp., Rhizopertha dominica, Sitophilus granarius, Sitophilus oryzae, Sitophilus zeamais, Stegobium paniceum;

from the order of the Diptera, e.g. Aedes aegypti, Aedes albopictus, Aedes taeniorhynchus, Anopheles spp., Calliphora erythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culex pipiens, Culex tarsalis, Drosophila carnicaisp., Fanca domestica spp., Simulium spp., Stomoxys calcitrans, Tipula paludosa;

from the class of Lepidoptera, e.g., Achroia grisella, Galleria mellonella, Plodia interpunctella, Tinea cloacella, Tinea pellionella, Tineola bisselliella;

from the class of the Siphonaptera, for example, Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis;

from the class of the Hymenoptera, e.g. Camponotus herculeanus, Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis, Paravespula spp., Tetramorium caespitum;

From the Anoplura order, e.g. Pediculus humanus capitis, Pediculus humanus corporis, Phthirus pubis; from the order Heteroptera, e.g. Cimex hemipterus, Cimex lectularius, Rhodinus prolixus, Triatoma infestans.

When used as household insecticides, these substances can also be used in combination with other known active ingredients, such as phosphoric acid esters, carbamates, pyrethroids, growth regulators or active ingredients from other known classes of insecticides.

The agents are used as aerosols, non-pressurized sprays, e.g. pump sprayers and spray devices, automatic misting machines, fuming devices, foams, gels, evaporation products with evaporation plates made of cellulose or plastic, liquid evaporators, gel and membrane evaporators, propeller driven evaporators, non-energy or passive evaporation systems, anti-moth papers, anti-moth bags and gels, as granules or dusting agents, in spreading baits or in stationary baits.

When the active compound combinations according to the invention are used, the application rates can be varied within wide limits, depending on the method of application. During the treatment of plant parts, the application rates of the active compound combinations are generally 0.1 to 10,000 g / ha, preferably 10 to 1000 g / ha.

The effective insecticidal and acaricidal activity of the active compound combinations according to the invention is apparent from the following examples. Whilst the individual active substances have certain shortcomings in their action, the combinations show an effect which exceeds a simple summation of actions.

A synergistic effect with insecticides and acaricides always exists if the action of an active compound combination is greater than the sum of the action of the active compounds applied separately.

The expected effect for a given combination of two active substances can be calculated according to

SR Colby, Weeds 15 (1967) 1, 20-22 as follows:

if

X is the mortality rate with the active ingredient

A in a dose of mg / ha or in a concentration of m ppm,

Y is the mortality rate with the active ingredient

B at a dose of ng / ha or in a concentration of n ppm, a

E is the mortality rate when the active substances A and B are used in doses of ming / ha or in a concentration of min ppm, then e = x + Y- Δ :!

100 the mortality rate is defined as%. Thus, 0% means the mortality rate corresponding to the control sample, and a mortality rate of 100% means that no paralysis is observed.

If the actual effect is greater than the calculated effect, the combination in its effect is superadditive, i.e. a synergistic effect exists. In this case, the actual observed mortality rate must be greater than the value for the expected mortality (E) calculated from the above formula.

Example A. Testing of Aphis gossypii

Solvent: 3 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To obtain a preferred active compound formulation, 1 part by weight of active compound is mixed with the stated amount of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

Cotton leaves (Gossypium hirsutum) heavily infested with cotton leaf aphid (Aphis gossypii) are immersed in the preparation of active substances of the desired concentration.

After the desired time has elapsed, the mortality rate is determined as%, where 100% means that all the aphids have been killed and 0% means that no aphids have been killed. The obtained values ​​of the mortality rate are converted according to the Colby formula.

In this test, for example, the following combination of active substances according to the present application shows a synergistically enhanced effect compared to the substances used separately.

PL 204 252 B1

TABLE A Part 1 Insects plant pests Testing of Aphis gossypii

<td>Active substances</td><td>Concentration of active substances in ppm</td><td colspan="2">Mortality rate in% after 6 days</td>

<td>Example I-10 known</td><td> 1,6</td><td colspan="2"> 0</td>

<td>Example II-a known</td><td> 1,6</td><td colspan="2"> 25</td>

<td>Example I-10 + example II-a (1: 1)</td><td rowspan="2"> 1,6 + 1,6</td><td>found. *</td><td>calculated **</td>

<td>according to the invention</td><td> 95</td><td> 25</td>

found * = operation found calculated ** = operation calculated according to the Colby formula

TABLE A Part 2 Insects plant pests Testing of Aphis gossypii

<td>Active substances</td><td>Concentration of active substances in ppm</td><td colspan="2">Mortality rate in% after 1 day</td>

<td>Example I-10 known</td><td> 8</td><td colspan="2"> 0</td>

<td>Example II-g known</td><td> 8</td><td colspan="2"> 70</td>

<td>Example I-10 + example II-g (1: 1)</td><td rowspan="2"> 8 + 8</td><td>found. *</td><td>calculated **</td>

<td>according to the invention</td><td> 95</td><td> 70</td>

found * = operation found calculated ** = operation calculated according to the Colby formula

Example B. Myzus Testing

Solvent: 3 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To obtain a preferred active compound formulation, 1 part by weight of active compound is mixed with the stated amount of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

Cabbage leaves (Brassica oleracea) heavily infested with peach and potato aphids (Myzus persicae) are immersed in the preparation of the active ingredient at the desired concentration.

After the desired time has elapsed, the mortality rate is determined as%, where 100% means that all pests have been killed and 0% means that no pest has been killed. The obtained values ​​of the mortality rate are converted according to the Colby formula.

In this test, for example, the following combination of active substances according to the present application shows a synergistically enhanced effect compared to the substances used separately.

TABLE B Part 1 Insects Plant Pests Myzus Testing

<td>Active substances</td><td>Concentration of active substances in ppm</td><td>Mortality rate in% after 6 days</td>

<td>Example I-10 known</td><td> 1,6</td><td> 5</td>

<td>Example II-k known</td><td> 1,6</td><td> 10</td>

<td>Example I-10 + example II-k (1: 1) according to the invention</td><td> 1,6+1,6</td><td>found * calculated ** 80 14.5</td>

found * = operation found calculated ** = operation calculated according to the Colby formula

PL 204 252 B1

TABLE B Part 2 Insects Plant Pests Myzus Testing

<td>Active substances</td><td>Concentration of active substances in ppm</td><td colspan="2">Mortality rate in% after 6 days</td>

<td>Example I-10 known</td><td> 1,6</td><td colspan="2"> 0</td>

<td>Example II-g known</td><td> 1,6</td><td colspan="2"> 10</td>

<td>Example I-10 + example II-g (1: 1)</td><td rowspan="2"> 1,6+1,6</td><td>found. *</td><td>calculated **</td>

<td>according to the invention</td><td> 95</td><td> 10</td>

found * = operation found calculated ** = operation calculated according to the Colby formula

Table B Part 3

Insects pests of plants

Myzus testing

<td>Active substances</td><td>Concentration of active substances in ppm</td><td colspan="2">Mortality rate in% after 1 day</td>

<td>Example I-10 known</td><td> 1,6</td><td colspan="2"> 0</td>

<td>Example 2 is known</td><td> 1,6</td><td colspan="2"> 15</td>

<td>Example I-10 + example II-m (1: 1)</td><td rowspan="2"> 1,6+1,6</td><td>found. *</td><td>calculated **</td>

<td>according to the invention</td><td> 45</td><td> 15</td>

found * = operation found calculated ** = operation calculated according to the Colby formula

Example C. Limit Concentration Testing / Soil Insects - Treatment of Transgenic Plants

Test insect: Diabrotica balteata - larvae in the soil

Solvent: 7 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To obtain a preferred active ingredient formulation, 1 part by weight of the active ingredient is mixed with the stated amount of solvent, the specified amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

The soil is poured on with the preparation of active ingredient, the concentration of the active ingredient in the formulation being practically irrelevant, only the amount by weight of active ingredient per unit volume of soil is decisive, expressed in ppm (mg / liter). The soil is filled into 0.25 liter pots and left at 20 ° C.

Immediately after treatment, pre-sprouted YIELD GUARD maize kernels (trademark of Monsanto Comp, USA) are introduced into each pot. After 2 days, the respective test insects are introduced into the treated soil. After a further 7 days, the degree of effect of the active ingredient is determined by counting the grown maize plants (1 plant = 20% effect).

Example D. Testing of Heliothis virescens - treatment of transgenic plants

Solvent: 7 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To obtain a preferred active compound formulation, 1 part by weight of active compound is mixed with the stated amount of solvent and the specified amount of emulsifier, and the concentrate is diluted with water to the desired concentration.

Soybean shoots (Glycine max) of Roundup Ready species (trademark of Monsanto Comp., USA) are immersed in the formulation of the active ingredient of the desired concentration and are planted with caterpillars of the Heliothis virescens tobacco flower while the leaves are still wet.

After the desired time has elapsed, the degree of mortality of the insects is determined.